WO2023074426A1 - Dispositif d'électrolyse - Google Patents

Dispositif d'électrolyse Download PDF

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Publication number
WO2023074426A1
WO2023074426A1 PCT/JP2022/038542 JP2022038542W WO2023074426A1 WO 2023074426 A1 WO2023074426 A1 WO 2023074426A1 JP 2022038542 W JP2022038542 W JP 2022038542W WO 2023074426 A1 WO2023074426 A1 WO 2023074426A1
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Prior art keywords
electrolytic solution
gas
carbon
electrolytic
lithium
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PCT/JP2022/038542
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English (en)
Japanese (ja)
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充康 今▲崎▼
幹人 杉山
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株式会社カネカ
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Priority to JP2023556327A priority Critical patent/JPWO2023074426A1/ja
Publication of WO2023074426A1 publication Critical patent/WO2023074426A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • the present invention relates to an electrolytic device capable of recovering lithium from seawater or the like and further reducing carbon dioxide.
  • Patent Document 1 In recent years, in order to reduce the emissions of carbon dioxide, which is a greenhouse gas, efforts have been made to generate carbon compounds from the emitted carbon dioxide and turn carbon dioxide into a resource (for example, Patent Document 1).
  • the electrochemical reaction device of Patent Document 1 includes an anode section, a cathode section, a separator for separating the anode section and the cathode section, and a power supply, and a voltage is applied between the anode section and the cathode section by the power supply.
  • Carbon dioxide can be reduced at the cathode to produce carbon compounds and hydrogen
  • water and hydroxide ions can be oxidized at the anode to produce oxygen and hydrogen ions.
  • Lithium has traditionally been mined in mines, but on the other hand, it is known that it is contained in large quantities in seawater. It is possible to reduce the cost of lithium.
  • an object of the present invention is to provide an electrolyzer capable of recovering lithium from seawater, brackish water, recycled waste liquid, etc. containing lithium ions, and generating a carbon compound from carbon dioxide.
  • the inventor uses a stock solution containing lithium ions as the electrolyte on the anode side, and uses a lithium ion conductive material that allows only lithium ions to move as the separator. Then, by applying a voltage between the anode and the cathode, while carbon dioxide is reduced at the cathode to produce a carbon compound, only lithium ions are transferred from the stock solution on the anode side to the cathode side by using the potential difference between the anode and the cathode. It was thought that lithium could be recovered from the recovered liquid while using the electric power for generating the carbon compound without waste.
  • One aspect of the present invention derived based on the above idea is a first electrode portion, a second electrode portion, a lithium ion exchange portion, a first electrolytic solution, and a second electrolytic solution containing lithium ions. and a first gas supply unit capable of supplying a first carbon gas containing carbon dioxide, wherein the first electrode unit includes a catalyst layer, the catalyst layer is in contact with the first electrolytic solution, and the first The two electrode portions are opposed to the first electrode portion with the lithium ion exchange portion interposed therebetween and are in contact with the second electrolytic solution, and the lithium ion exchange portion is provided with the first electrolytic solution and the second electrolytic solution.
  • Carbon compounds here refer to compounds containing carbon, and include not only organic compounds but also oxides such as carbon monoxide, carbonates, and carbides. The same shall apply hereinafter.
  • the lithium ions contained in the second electrolytic solution pass through the lithium ion exchange section, move to the first electrolytic solution, and are concentrated in the first electrolytic solution. Therefore, by adding a precipitant or the like, the lithium ions in the first electrolytic solution can be precipitated, and lithium can be recovered.
  • the carbon compound can be produced by reducing the carbon dioxide of the first carbon gas, so that the carbon compound can be produced while consuming carbon dioxide.
  • the first electrode section has the catalyst layer laminated on the gas diffusion electrode, and the first gas supply section includes the first carbon gas diffusion electrode on the opposite side of the gas diffusion electrode from the catalyst layer. It is to supply gas.
  • the gas diffusion electrode since the gas diffusion electrode is used, hydrogen is less likely to be generated on the first electrode portion, and more carbon compounds can be generated.
  • the lithium ion exchange part is a lithium ion conductive solid electrolyte.
  • the lithium ion exchange part is made of a solid electrolyte, the durability is higher than when a resin ion exchange membrane is used.
  • the second electrolytic solution contains lithium chloride or lithium sulfate.
  • the second electrolytic solution is seawater.
  • seawater is used as the second electrolytic solution, lithium can be recovered at low cost.
  • chloride ions are included, chlorine can also be generated on the second electrode portion.
  • the first electrolytic solution is an alkaline aqueous solution.
  • the reduction reaction of carbon dioxide can proceed efficiently.
  • the first electrolytic solution contains a lithium hydroxide aqueous solution.
  • impurities are less likely to be generated in the first electrolytic solution.
  • a preferred aspect is to provide a second gas supply section for supplying a second carbon gas containing carbon dioxide to the first electrolytic solution.
  • lithium can be recovered as a precipitate of lithium carbonate.
  • the carbon compound is a C1 compound or a C2 compound.
  • C1 compound refers to a carbon compound having one carbon atom, such as methane, carbon monoxide, and methanol.
  • C2 compound refers to a carbon compound having two carbon atoms, such as ethane, ethanol, and ethylene.
  • lithium can be recovered from seawater and waste liquid containing lithium ions, and carbon compounds can be produced from carbon dioxide.
  • FIG. 2 is a cross-sectional view conceptually showing an electrolysis apparatus according to a second embodiment of the present invention
  • FIG. 3 is a cross-sectional view of the electrolysis device of FIG. 2 in an electrolysis step
  • FIG. 3 is a cross-sectional view of the electrolytic device of FIG. 2 in a deposition step
  • the electrolytic device 1 of the first embodiment of the present invention recovers lithium from an electrolytic solution 8 such as seawater or waste liquid containing lithium ions, and further produces a carbon compound different from carbon dioxide from a first carbon gas containing carbon dioxide. It is something to do.
  • the electrolytic device 1 includes an electrolytic cell 2, a first electrode section 3, a second electrode section 5, a lithium ion exchange section 6, a first electrolytic solution 7, and a second electrolytic solution 8.
  • a first gas supply unit 10 a second gas supply unit 11, a first gas discharge unit 12, a second gas discharge unit 13, a third gas discharge unit 14, an electrolytic solution introduction unit 15, a first It has an electrolytic solution discharge part 16, a second electrolytic solution discharge part 17, and a power supply part 18, and the inside of the electrolytic cell 2 is divided into three spaces 20 to 22 by the first electrode part 3 and the lithium ion exchange part 6. It is
  • the first electrode part 3 is a cathode electrode that reduces the first carbon gas containing carbon dioxide, and is resistant to the first electrolytic solution 7 .
  • the first electrode portion 3 is formed by laminating a catalyst layer 31 on a gas diffusion electrode 30. As shown in FIG.
  • the gas diffusion electrode 30 is a porous base material having electrical conductivity, and is capable of permeating gas in the thickness direction.
  • the catalyst layer 31 is composed of one or more catalysts, and can reduce carbon dioxide to C1 compounds and/or C2 compounds (carbon compounds) depending on the type of catalyst.
  • Ni—NC, Ag, Ag—S—C 3 N 4 /CNT, CoPc—CN/CNT, CoO x /CNT, etc. are used when carbon monoxide, which is a C1 compound, is generated. can.
  • the catalyst layer 31 can be made of Sn, Bi, SnO 2 /CNT or the like when producing formate which is a C1 compound.
  • Cu 2 O/ZnO or the like can be used for the catalyst layer 31 when methanol, which is a C1 compound, is generated.
  • Cu 2 S/Cu—V, CuZn, or the like can be used when ethanol, which is a C2 compound, is produced.
  • the second electrode portion 5 is a counter electrode that forms a pair with the first electrode portion 3 and is an anode electrode that oxidizes the second electrolytic solution 8 .
  • the second electrode part 5 is an electrode that is resistant to the second electrolytic solution 8 and corrosion resistant to chlorine, and a metal electrode such as a platinum electrode can be used.
  • the lithium ion exchange section 6 is a cation exchange section that has lithium ion conductivity and allows lithium ions to move only from the second electrolytic solution 8 side to the first electrolytic solution 7 side.
  • the lithium ion exchange part 6 is not particularly limited as long as it has lithium ion conductivity.
  • Lithium ion conductive solid electrolytes such as LATP (lithium aluminum titanium phosphate) having a NASICON-type crystal structure and LLTO (lithium lanthanum titanate) having a perovskite-type crystal structure can be used for the lithium ion exchange unit 6, for example.
  • the lithium ion exchange part 6 may be composed of a resinous lithium ion conductive material such as a cation exchange membrane, but is preferably composed of a lithium ion conductive solid electrolyte from the viewpoint of durability.
  • the lithium ion exchange part 6 has a surface on which lithium ions move into the lithium ion conductive solid electrolyte and lithium ions move from the lithium ion conductive solid electrolyte.
  • a buffer layer may be formed to promote the
  • the lithium ion exchange part 6 may be a composite of solid electrolyte and polymer membrane, or may be a metal organic framework.
  • the lithium ion exchange unit 6 may contain an adsorbent that selectively adsorbs specific ions other than lithium ions.
  • the first electrolytic solution 7 does not substantially react with lithium ions and can maintain lithium ions in an ionic state. or an acidic aqueous solution such as hydrochloric acid (HCl) can be used.
  • the first electrolytic solution 7 of the present embodiment is preferably lithium hydroxide from the viewpoint of depositing lithium carbonate A with the second carbon gas.
  • the second electrolytic solution 8 contains a lithium salt and is maintained as lithium ions in a liquid such as an aqueous solution, an organic solvent, or an ionic liquid.
  • a liquid such as an aqueous solution, an organic solvent, or an ionic liquid.
  • seawater containing lithium ions recycled waste liquid such as waste liquid from lithium ion secondary batteries, treated water of lithia ore, brackish water unsuitable for lithium production, or the like can be used.
  • the lithium salt contained in the second electrolytic solution 8 include lithium chloride and lithium sulfate.
  • the second electrolytic solution 8 of the present embodiment uses seawater and contains lithium chloride as a lithium salt.
  • the first gas supply part 10 is a part that supplies a first carbon gas containing carbon dioxide to the first space 20 .
  • the first carbon gas is a gas whose main component is carbon dioxide, and carbon dioxide preferably accounts for 80% or more of the total components, and more preferably carbon dioxide accounts for 95% or more of the total components.
  • main component refers to a component that accounts for more than 50% of the total. The same shall apply hereinafter.
  • the second gas supply part 11 is a part that supplies a second carbon gas containing carbon dioxide to the second space 21, and has a nozzle extending vertically in a cylindrical shape.
  • the second carbon gas is a gas whose main component is carbon dioxide, and carbon dioxide preferably accounts for 80% or more of the total components, and more preferably carbon dioxide accounts for 95% or more of the total components.
  • the first gas discharge part 12 is a part that discharges gas from the first space 20 to an external storage tank (not shown), and discharges gas (for example, carbon dioxide, carbon compounds, etc.) in the first space 20 to the outside. can be discharged into a storage tank.
  • the second gas discharge part 13 is a part that discharges gas from the second space 21 to an external storage tank (not shown), and removes gas (for example, carbon dioxide, carbon compounds, hydrogen, etc.) in the second space. It can be discharged to an external storage tank.
  • the third gas discharge part 14 is a part that discharges gas from the third space 22 to an external storage tank (not shown), and discharges the gas (for example, chlorine, oxygen, etc.) in the third space to the external storage tank. can be discharged to
  • the electrolytic solution introduction part 15 is a part that introduces the second electrolytic solution 8 into the third space 22 from an external electrolytic solution supply source (not shown).
  • the first electrolytic solution discharge part 16 is a part for discharging the first electrolytic solution 7 from the second space 21 to an external storage tank (not shown).
  • the first electrolyte solution discharge part 16 is placed in an external storage tank (not shown) so that the first electrolyte solution 7 does not exceed a predetermined level. It is possible to discharge the first electrolytic solution 7 .
  • the second electrolytic solution discharge part 17 is a part for discharging the second electrolytic solution 8 from the third space 22 to an external storage tank (not shown).
  • the second electrolytic solution discharge part 17 discharges the second electrolytic solution 8 to the outside so that the second electrolytic solution 8 does not exceed a predetermined level. It is possible.
  • the power supply section 18 is a section that applies a predetermined voltage between the first electrode section 3 and the second electrode section 5 .
  • the power supply unit 18 may apply voltage using commercial power, or may apply voltage using renewable energy generated by a power supply unit such as a solar cell or a fuel cell.
  • the first space 20 is a space forming a first gas flow path of the first carbon gas from the first gas supply section 10 to the first gas discharge section 12, and the first gas supply section 10 and the first gas discharge section A part between 12 is a space partitioned by the first electrode part 3 .
  • the second space 21 is a space separated from the first space 20 by the first electrode section 3 and separated from the third space 22 by the lithium ion exchange section 6 .
  • the third space 22 is a space separated from the second space 21 by the lithium ion exchange section 6 .
  • the first electrode section 3 faces the second electrode section 5 with the lithium ion exchange section 6 interposed therebetween.
  • the electrode units 3 and 5 stand upright from the bottom surface of the electrolytic cell 2 toward the top surface, and the catalyst layer 31 side of the first electrode unit 3 faces the lithium ion exchange unit 6. are doing. That is, the first electrode portion 3 is exposed to the first space 20 on the side of the gas diffusion electrode 30 and exposed to the second space 21 on the side of the catalyst layer 31 .
  • the first gas supply part 10 is provided below the first gas discharge part 12 in the first space 20, and the first carbon gas is supplied from the first gas supply part 10 to the first space 20.
  • a first gas passage leading to the first gas discharge portion 12 is formed through the .
  • the gas diffusion electrode 30 of the first electrode section 3 is exposed in the middle of the first gas flow path.
  • the second gas supply part 11 extends from the top surface of the electrolytic cell 2 to the vicinity of the bottom surface in the second space 21, and the second gas discharge part 13 is provided on the top surface of the electrolytic cell 2, A first electrolytic solution discharge part 16 is provided on the side surface of the electrolytic bath 2 . That is, the electrolytic device 1 is formed with a second gas flow path that leads the second carbon gas from the second gas supply part 11 to the second gas discharge part 13 by folding back near the bottom surface, and the first electrolytic solution 7 When the second space 21 is filled up to the height of the first electrolytic solution discharge portion 16 , part of the first electrolytic solution 7 is discharged from the first electrolytic solution discharge portion 16 to the outside. Further, in the electrolytic device 1, the catalyst layer 31 of the first electrode portion 3 is exposed in the middle of the second gas flow path.
  • the third gas discharge part 14 is provided on the top surface of the electrolytic cell 2 in the third space 22, the electrolytic solution introduction part 15 is provided on the bottom surface of the electrolytic cell 2, and the second electrolytic solution A discharge part 17 is provided on the side of the electrolytic cell 2 .
  • the second electrolytic solution 8 introduced from the electrolytic solution introduction part 15 fills the third space 22 up to the height of the second electrolytic solution discharge part 17, part of the second electrolytic solution 8 is discharged into the second electrolytic solution.
  • the liquid is discharged from the liquid discharge portion 17 to an external storage tank.
  • the electrolysis method of the electrolysis device 1 of this embodiment includes an electrolysis step and a deposition step.
  • the electrolysis step may be performed concurrently with the deposition step, or may be performed separately.
  • the case where the electrolysis process and the deposition process are performed separately and independently, and the deposition process is performed after the electrolysis process will be described.
  • Electrolysis process In the electrolysis step, a voltage is applied between the first electrode portion 3 and the second electrode portion 5 by the power supply portion 18, and the carbon dioxide in the first carbon gas is reduced on the first electrode portion 3 to generate a carbon compound. , and the chloride ions are oxidized on the second electrode portion 5 to generate chlorine gas. Specifically, due to the potential difference between the first electrode portion 3 and the second electrode portion 5 generated by the power supply portion 18, the chloride ions around the second electrolytic solution 8 are oxidized, and the lithium ions in the second electrolytic solution 8 are The lithium ions pass through the lithium ion exchange section 6 and reach the first electrolytic solution 7 , where the lithium ions are concentrated.
  • the carbon dioxide in the first carbon gas passing through the first gas flow path, the catalyst layer 31, and the three-layer interface of the first electrolytic solution 7 are reduced, and the carbon dioxide is reduced.
  • a compound is produced.
  • the carbon compound generated on the first electrode part 3 is water-soluble, it dissolves in the first electrolytic solution 7 and accumulates in the first electrolytic solution 7, and the carbon compound generated on the first electrode part 3
  • the carbon compound is water-insoluble, it passes through the first gas channel and is discharged from the first gas discharge part 12 to an external storage tank, or passes through the second gas channel and is discharged as the second gas. It is discharged from the part 13 to an external storage tank.
  • lithium ions in the second electrolytic solution 8 move to the first electrolytic solution 7 as the reaction progresses, and the concentration of lithium ions in the first electrolytic solution 7 increases.
  • concentration in the first electrolytic solution 7 reaches a certain concentration, the electrolysis step is stopped or terminated, and the deposition step is started.
  • the second carbon gas is introduced into the first electrolytic solution 7 and the second carbon gas and the first electrolytic solution 7 are reacted to deposit lithium carbonate A.
  • the second carbon gas is supplied from the second gas supply unit 11 to the first electrolytic solution 7 in which lithium ions are concentrated in the electrolysis step.
  • lithium hydroxide (lithium ions and hydroxide ions) occupying the first electrolytic solution 7 reacts with carbon dioxide, and lithium carbonate A is deposited, as shown in the following reaction formula.
  • CO 2 +2Li + +2OH ⁇ ⁇ Li 2 CO 3 +H 2 O When the lithium carbonate A is sufficiently produced, the deposition step is stopped or terminated, and if necessary, the electrolysis step is started.
  • the above electrolysis process and deposition process are repeated as necessary to reduce the carbon dioxide of the first carbon gas to a carbon compound and recover lithium as lithium carbonate A.
  • the lithium ions contained in the second electrolytic solution 8 pass through the lithium ion exchange section 6 to move to the first electrolytic solution 7, and the lithium ions in the first electrolytic solution 7 is concentrated, lithium can be recovered by precipitating the lithium ions in the first electrolytic solution 7 with a precipitant or the like.
  • carbon dioxide in the first carbon gas can be reduced to produce a carbon compound, so carbon compounds can be produced while consuming carbon dioxide.
  • the electrolytic device 1 of the first embodiment since seawater is used as the second electrolytic solution 8, the environmental load is small and lithium can be recovered at low cost. Chlorine gas can also be generated.
  • the carbon dioxide in the second carbon gas functions as a precipitant for precipitating the lithium ions in the first electrolytic solution 7, more carbon dioxide can be consumed. can.
  • the water-soluble carbon compound dissolves in the first electrolytic solution 7 and the water-insoluble carbon compound is discharged from the first gas discharge portion 12 . Therefore, the produced carbon compound can be separated into water-soluble and water-insoluble.
  • the electrolysis device 100 includes an electrolysis section 102, a deposition section 103, a first path 105, and a second path 106.
  • the electrolysis section 102, the first path 105, and the deposition section 103 , and the second path 106 form an annular circulation flow path 107 .
  • the electrolytic section 102 includes an electrolytic cell 2, a first electrode section 3, a second electrode section 5, a lithium ion exchange section 6, a first electrolytic solution 7, a second electrolytic solution 8, and a first gas supply section. 10, a first gas discharge portion 12, a second gas discharge portion 13, a third gas discharge portion 14, a first electrolytic solution introduction portion 110, a second electrolytic solution introduction portion 15, and a first electrolytic solution discharge It has a portion 16 , a second electrolytic solution discharge portion 17 and a power supply portion 18 .
  • the first electrolytic solution introduction part 110 is provided on the bottom surface of the electrolytic bath 2 and is a part that introduces the first electrolytic solution 7 into the second space 21 from the second path 106 .
  • the first electrolytic solution discharge part 16 is a part for discharging the first electrolytic solution 7 from the second space 21 to the first path 105 .
  • the deposition section 103 includes a deposition tank 120, a third electrolyte introduction section 121, a second gas supply section 122, and a third electrolyte discharge section 123, as shown in FIG.
  • the third electrolytic solution introduction part 121 is a part that introduces the first electrolytic solution 7 from the second space 21 into the deposition tank 120 via the first path 105 .
  • the second gas supply unit 122 like the second gas supply unit 11 of the first embodiment, is a part that supplies a second carbon gas containing carbon dioxide to the deposition tank 120, and has a cylindrical nozzle extending vertically. I have.
  • the third electrolytic solution discharge part 123 is a part for discharging the first electrolytic solution 7 from inside the deposition tank 120 to the second path 106 .
  • the first path 105 is a connection pipe that connects the first electrolytic solution discharge portion 16 of the electrolytic portion 102 and the third electrolytic solution introduction portion 121 of the deposition portion 103, and has an on-off valve 130 in the middle.
  • the second path 106 is a connection pipe that connects the third electrolytic solution discharge portion 123 of the deposition portion 103 and the first electrolytic solution introduction portion 110 of the electrolytic portion 102, and has an on-off valve 131 and a circulation pump 132 in the middle.
  • the circulation pump 132 can supply the first electrolytic solution 7 downstream at a predetermined flow rate.
  • the electrolytic device 100 of the second embodiment includes an electrolytic process and a deposition process. It is different from the electrolytic device 1 of the embodiment.
  • the on-off valves 130 and 131 are opened, the circulation pump 132 is driven, and the first electrolytic solution 7 in the deposition tank 120 is discharged through the second path 106 to the first electrolytic solution.
  • the first electrolytic solution 7 introduced into the second space 21 from the introduction portion 110 and introduced from the first electrolytic solution introduction portion 110 overflows the first electrolytic solution discharge portion 16, and the first electrolytic solution 7 is It is introduced into the deposition tank 120 from the third electrolytic solution introduction part 121 via the path 105 .
  • the first electrolytic solution 7 in the deposition tank 120 is replaced with the first electrolytic solution 7 containing a high concentration of lithium ions, and the second carbon gas is supplied to the first electrolytic solution 7 from the second gas supply unit 122. supply. Then, lithium hydroxide (lithium ions and hydroxide ions) occupying the first electrolytic solution 7 reacts with carbon dioxide, and lithium carbonate A is deposited. When sufficient lithium carbonate A is produced, the precipitation process is stopped or terminated.
  • the electrolytic bath 2 and the deposition bath 120 are provided separately, and lithium is deposited as lithium carbonate A in the deposition bath 120 outside the electrolytic bath 2 . Therefore, lithium can be recovered in the deposition tank 120 without stopping the electrolysis process in the electrolysis unit 102 .
  • lithium is recovered by circulating the first electrolytic solution 7 in the circulation flow path 107, so lithium can be recovered at low cost.
  • carbon dioxide was used as a precipitating agent for precipitating lithium carbonate A, but the present invention is not limited to this. Other precipitants may be used.
  • the electrolytic process and the deposition process are separate and independent processes, but the present invention is not limited to this.
  • the electrolytic process and the deposition process are performed in parallel, but the present invention is not limited to this. You may perform an electrolysis process and a deposition process separately.
  • the first electrolytic solution 7 is returned from the deposition portion 103 to the electrolytic portion 102 through the second path 106, but the present invention is not limited to this.
  • the first electrolytic solution 7 for which the deposition step has been completed may be directly discharged to an external storage tank.
  • the second path 106 is connected to an external electrolytic solution supply source, and the first electrolytic solution 7 is supplied from the electrolytic solution supply source into the second space 21 of the electrolytic section 102 through the first electrolytic solution introduction portion 110. is preferred.
  • the second carbon gas containing carbon dioxide is supplied from the second gas supply units 11 and 122 to the second space 21 or the deposition tank 120 to deposit lithium as lithium carbonate A, but the present invention It is not limited to this.
  • a precipitant other than the second carbon gas may be added from the second gas supply units 11 and 122 to deposit lithium as a lithium precipitate.
  • the second gas supply unit 11, 122 functions as a precipitant supply unit that supplies a solid, liquid, or gaseous precipitant.
  • each constituent member can be freely replaced or added between the embodiments.

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Abstract

L'invention concerne un dispositif d'électrolyse capable de collecter du lithium à partir de l'eau de mer, de l'eau saumâtre, d'effluent recyclé, et analogues qui contiennent des ions lithium, et capable de générer un composé carboné à partir de dioxyde de carbone.　Le dispositif d'électrolyse comprend une première partie d'électrode, une seconde partie d'électrode, une partie d'échange d'ions lithium, une première solution électrolytique, une seconde solution électrolytique qui contient des ions lithium, et une première partie d'alimentation en gaz apte à fournir un premier gaz carboné comprenant du dioxyde de carbone. La première partie d'électrode comprend une couche de catalyseur. La couche de catalyseur est en contact avec la première solution électrolytique. La seconde partie d'électrode fait face à la première partie d'électrode avec la partie d'échange d'ions lithium entre celles-ci et est en contact avec la seconde solution électrolytique. La partie d'échange d'ions lithium est disposée de manière à séparer la première solution électrolytique de la seconde solution électrolytique, et permet sélectivement le passage d'ions lithium de la seconde solution électrolytique à la première solution électrolytique. Le dispositif électrolytique est conçu pour, en appliquant une tension entre la première partie d'électrode et la seconde partie d'électrode tout en fournissant le premier gaz carboné de la première partie d'alimentation en gaz à la première partie d'électrode, réduire le dioxyde de carbone dans le premier gaz carboné et générer un composé carboné différent du dioxyde de carbone.
PCT/JP2022/038542 2021-10-26 2022-10-17 Dispositif d'électrolyse WO2023074426A1 (fr)

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JP2021174960 2021-10-26
JP2021-174960 2021-10-26

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